Ice Nucleation by Alcohols Arranged in Monolayers at the Surface of Water Drops

Monolayers of aliphatic long-chain alcohols induced nucleation of ice at temperatures approaching 0 degrees C, in contrast with water-soluble alcohols, which are effective antifreeze agents. The corresponding fatty acids, or alcohols with bulky hydrophobic groups, induce freezing at temperatures as much as 12 degrees C lower. The freezing point induced by the amphiphilic alcohols was sensitive not only to surface area per molecule but, for the aliphatic series (C(n)H(2n + 1)OH), to chain length and parity. The freezing point for chains with n odd reached an asymptotic temperature of 0 degrees C for an upper value of n = 31; for n even the freezing point reached a plateau of -8 degrees C for n in the upper range of 22 to 30. The higher freezing point induced by the aliphatic alcohols is due to formation of ordered clusters in the uncompressed state as detected by grazing incidence synchrotron x-ray diffraction measurements. The diffraction data indicate a close lattice match with the ab layer of hexagonal ice.